Work

Engineering PtFe/LiO2 Frontier Orbital Interaction in Li–O2 Batteries

Year: 2026

Type: article

Abstract: Elucidating the structure–activity relationship between the electronic structure of catalytic active sites and oxygen evolution reaction (OER) activity at the orbital level is critical yet challenging in lithium–oxygen (Li–O 2 ) batteries. Herein, employing frontier molecular orbital theory, we designed a Pt-based catalyst as a model cathode to investigate the influence of frontier orbital interactions between the Pt d z 2 orbital and the 5 σ orbital of LiO 2 on the OER activity. Specifically, compared to the pure Pt catalyst, the d z 2 – d z 2 orbital coupling between low-electronegativity Fe and Pt in PtFe catalyst induces predominant electron transfer from Fe to the d z 2 frontier orbital of Pt. As the Pt content in PtFe alloys increases progressively (from Pt 58 Fe 42 , Pt 67 Fe 33 to Pt 76 Fe 24 ), the electron population of the Pt 5 d z 2 orbital gradually decreases (1.92 for Pt 58 Fe 42 , 1.85 for Pt 67 Fe 33 , and 1.80 for Pt 76 Fe 24 ). This leads to a gradual enhancement in the strength of interactions between the Pt d z 2 orbital and the frontier orbitals of LiO 2 , consequently resulting in a progressive decline in the OER catalytic activity. Establishing the correlating between the electron population in the d z 2 frontier orbital and OER activity provides a descriptor for designing efficient electrocatalysts in Li–O 2 batteries.

Source: Nano-Micro Letters

DOI: 10.1007/s40820-026-02085-z